TW201610023A - Composition for making hard coating layer - Google Patents

Abstract

The present invention relates to a composition for forming a hard coating layer, and more specifically, to a composition for forming a hard coating layer which includes an epoxy siloxane resin having a weight average molecular weight in the range of 2,000 to 15,000 and a polydispersity index (PDI) in the range of 2.0 to 4.0, and thus which may form a hard coating layer having significantly improved hardness as well as excellent flexibility such that bending deformation is minimized.

Description

Composition for making a hard coat layer [Priority statement]

The present application claims priority to and claims the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the disclosure.

This invention relates to a composition for forming a hard coat layer.

Recently, a thin display device using a flat panel display device such as a liquid crystal display device, an organic light emitting diode display device or the like has been attracting attention. In particular, the thin display devices are constructed in the form of a touch screen panel and are widely used in many smart devices characterized by a portable type, such as a smart phone, a tablet, Personal computers and a wide range of wearable devices.

The portable display device based on a touch screen panel includes a window substrate for protecting the display panel to protect a display panel from scratches or external impact. In most cases, a tempered glass for a display is used as the window substrate. The tempered glass for display is thinner than ordinary glass, but has high strength and scratch resistance.

However, one of the weights of the tempered glass is not suitable for reducing the weight of the portable device. Moreover, the tempered glass is damaged by being susceptible to external impact, so that it is difficult to achieve non-breaking characteristics. The tempered glass can only be bent to a limited extent and is therefore not suitable as a material for a flexible display that is flexible and foldable.

Recently, various studies have been conducted on optical plastic substates that ensure flexibility and impact resistance and have the same strength or scratch resistance as those of tempered glass. In general, examples of such optical plastic substrates that are more flexible than tempered glass include polyethylene terephthalate (PET), polyethersulfone (PES), polyethylene naphthalate. (polyethylene naphthalate, PEN), polyacrylate (PAR), polycarbonate (PC), polyimide (PI), and the like. However, compared with tempered glass which is a window substrate for protecting a display, the polymer plastic substrates exhibit insufficient physical properties such as hardness and scratch resistance, and thus have insufficient impact resistance. Therefore, many attempts have been made to complement these physical properties by coating the plastic substrates with a composite resin composition.

In a conventional hard coating process, a resin comprising a photocurable functional group (for example, an acrylate group, an epoxy group or the like) and a curing agent or a curing catalyst are used. A composition of one of the reactive additives. In particular, when the optical plastic base material film is coated with a composite resin having a high functional group, the composite resin has improved hardness and scratch resistance and can be used as a window substrate for protecting the display.

However, in the case of a conventional photocurable composite resin having a high functional group of one of an acrylate or an epoxy group, it is difficult to achieve the same high hardness as that of the tempered glass, and it may occur due to shrinkage when the resin is cured. Large bending deformation (curling). The flexibility is also insufficient, so the resins are not suitable for application to a flexible display as a window substrate for protecting a display. A plastic substrate is disclosed in Korean Patent Application Publication No. 2013-74167.

[Patent Literature]

Korean Patent Application Publication No. 2013-74167

The present invention is directed to providing a composition which can form a hard coat layer having a significantly improved hardness.

The present invention is directed to providing a composition which can form one of the hard coat layers having excellent flexibility.

The present invention is directed to providing a base material having one of the hard coat layers.

According to one aspect of the present invention, there is provided a composition for forming a hard coat layer comprising a weight average molecular weight in the range of 2,000 to 15,000 and a polydispersity index in the range of 2.0 to 4.0. (polydispersity index, PDI) One of the epoxy oxirane resins.

The decane resin may have a weight average molecular weight in the range of 5,000 to 15,000.

The decane resin may have an epoxy equivalent in the range of from 3.0 millimoles per gram to 6.3 millimoles per gram.

The silicone resin alumoxane can be prepared by the hydrolysis of alkoxy silane-one represented by the following formula 1 and one of a condensation reaction: [Formula _{^{1] R 1 n Si (OR}} 2) 4-n

(wherein R ¹ is an epoxycycloalkyl group having one to three carbon atoms, or a straight chain having one to six carbon atoms and substituted with an oxiranyl group; A branched alkyl group which may be heteroatomized, R ² is a straight or branched alkyl group having 1 to 7 carbon atoms, and n is an integer in the range of 1 to 3.

The alkoxydecane represented by Formula 1 may be at least one type selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4- Epoxycyclohexyl)ethyltriethoxydecane and 3-glycidoxypropyltrimethoxysilane.

The decane resin can be produced by hydrolysis and condensation reaction of the alkoxy decane represented by Formula 1 and one alkoxy decane represented by the following formula 2: [Formula 2] R ³ _m Si (OR ⁴ ) _4-m

(wherein R ³ includes at least one functional group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and having 3 to One of 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, an acrylic group, or a methacrylic group ), halo, amine, mercapto, ether, ester, carbonyl, carboxyl, vinyl, nitro, sulfone group and alkyd group, R ⁴ is from 1 to 7 The carbon atoms have a straight chain or a branched alkyl group, and m is an integer in the range of 0 to 3.

The composition for forming a hard coat layer may further comprise 0.1 parts by weight to 10 parts by weight of one of the polymerization initiators and 20 parts by weight to 70 parts by weight based on 109 parts by weight of the epoxy oxirane resin. Solvent.

According to another aspect of the present invention, there is provided a hard coat film comprising a base material, at least one surface of which has a hard coat layer formed from the above composition.

The base material may be selected from at least one resin selected from the group consisting of a polyester resin, a cellulose resin, a polycarbonate resin, an acrylic resin, a styrene resin, and a A polyolefin resin, a polyamidene resin, a polyether oxime resin, and a fluorene-based resin.

100‧‧‧hard coating

110‧‧‧Basic materials

120‧‧‧hard coating

R ₁ , R ₂ ‧‧‧ bottom radius

The above and other objects, features and advantages of the present invention will become more apparent to those skilled in the <RTIgt A schematic cross-sectional view of a base material comprising a hard coat formed from a composition for forming a hard coat layer according to an embodiment of the present invention; FIG. 2 is a schematic illustration Performing an embodiment of a bending test for a base material, the base material comprising a hard coat layer formed by forming a composition of a hard coat layer according to an embodiment of the present invention; and a third The illustration schematically illustrates an embodiment of a bending test performed on a base material comprising a hard coat formed from a composition for forming a hard coat layer in accordance with an embodiment of the present invention.

Exemplary embodiments of the present invention will be described in detail below with reference to the accompanying drawings. While the invention has been shown and described with reference to the embodiments

The present invention relates to a composition for forming a hard coat layer which can form a hard coat layer having significantly improved hardness and excellent flexibility such that bending deformation is minimized.

Hereinafter, the present invention will be explained in detail.

Composition for forming a hard coat layer

According to an embodiment of the present invention, the composition for forming a hard coat layer comprises one of a polydispersity index (PDI) having a weight average molecular weight in the range of 2,000 to 15,000 and a range of 2.0 to 4.0. Epoxy oxirane resin.

In the present invention, the epoxy oxirane resin refers to a oxirane resin having one epoxy group, and the epoxy group may be an alicyclic epoxy group or an aliphatic epoxy group. An aromatic epoxy group or a mixture thereof.

According to an embodiment of the present invention, since an epoxy oxirane resin having a weight average molecular weight and a polydispersity index in a specific range is used in a composition for forming a hard coat layer, the hard coat can be remarkably improved. The hardness of the layer. In addition, the flexibility is considerably enhanced, thereby suppressing bend modification.

The epoxy siloxane resin has a weight average molecular weight in the range of 2,000 to 15,000. When the weight average molecular weight is less than 2,000, the desired hardness of the hard coat layer cannot be achieved, and ductility is exhibited. When the weight average molecular weight is more than 15,000, a desired physical property, that is, a high hardness of the hard coat layer, can be obtained, but the workability required in the film treatment is deteriorated. Consider hard The hardness and workability of the coating, preferably the weight average molecular weight, may range from 5,000 to 15,000.

The epoxy oxirane resin has a polydispersity index (PDI) in the range of 2.0 to 4.0. When the polydispersity index is less than 2.0, it is difficult to satisfy the two physical properties of hardness and ductility of the hard coat layer. When the polydispersity index is more than 4.0, the physical property of ductility is excessively exhibited.

The epoxy equivalent of the epoxy oxirane resin is not particularly limited and may be, for example, in the range of from 3.0 mmol/g to 6.3 mmol/g. When the epoxy equivalent is in the above range, a compact cross-linking network can be formed, and the hardness can be remarkably improved.

According to an embodiment of the present invention, the epoxy oxirane resin may be prepared by hydrolysis and condensation reaction of a free alkoxy decane having one epoxy group, or may have an epoxy group. The monoalkoxydecane and a different type of alkoxydecane are prepared by hydrolysis and condensation reaction in the presence of water.

The following Reaction Formula 1 to Reaction Scheme 3 schematically show the hydrolysis and condensation reaction of alkoxydecane in the presence of water and a catalyst.

[Reaction formula 3]

In Reaction Formula 1 to Reaction Formula 3, R may be a straight chain or branched alkyl group having 1 to 7 carbon atoms, and R' may include at least one functional group selected from the group consisting of: a straight or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, having 2 to 20 One of a carbon atom, an alkynyl group, and an aryl group, an acryl group, a methacryl group, a halogen group, an amine group, a decyl group, an ether group, an ester group, a carbonyl group, a carboxyl group, a vinyl group, a nitro group, a fluorenyl group, and having 6 An alkyd group of up to 20 carbon atoms, which includes an epoxy group.

Reaction Scheme 1 shows that one of the starting materials alkoxydecane is hydrolyzed by water to form a monohydroxy group. As can be seen from the reaction formula 2 or the reaction formula 3, the hydroxyl group thus formed forms a monooxane bond by condensation reaction with one of the hydroxyl groups or the monoalkylene group of the other decane. Therefore, when the rate of the reaction is adjusted, the weight average molecular weight and polydispersity index (PDI) of the finally formed alkoxylate compound can be adjusted. The reaction temperature, the amount and type of the catalyst, a solvent and the like are also a major factor.

A catalyst is used to prepare an epoxy oxirane resin having a weight average molecular weight in the range of 2,000 to 15,000 and a polydispersity index in the range of 2.0 to 4.0 by means of the reaction formula. Examples of the catalyst that can be used include an acid catalyst such as hydrochloric acid, acetic acid, hydrogen fluoride, nitric acid, sulfuric acid, chlorosulfonic acid, iodic acid, pyrophosphoric acid, and the like; a base catalyst such as ammonia, potassium hydroxide, hydrogen Sodium oxide, cesium hydroxide, imidazole, n-butylamine, di-n-butylamine, tri-n-butylamine, ammonium perchlorate, tetramethylammonium hydroxide, and the like; an ion exchange resin such as Amberite IRA -400, IRA-67 and the like; and mixtures thereof.

Although the amount of the catalyst is not particularly limited, it is based on about 100 parts by weight of the alkoxy group. The acid catalyst or the base catalyst may be added in an amount of about 0.0001 part by weight to 0.01 part by weight, and the ion exchange resin may be added in an amount of about 1 part by weight to 10 parts by weight, but the invention is not limited thereto.

The hydrolysis and condensation reaction may be carried out at room temperature for about 12 hours to about 7 days while stirring, and may be stirred at about 60 ° C to 100 ° C for about 2 hours to 72 hours to promote the reaction, but is not limited thereto.

As can be seen from the reaction formula 1 to the reaction formula 3, when the reaction is started, alcohol and water are produced as by-products. When the by-products are removed, a reverse reaction can be reduced while inducing a forward reaction, and thus the rate of the reaction can be adjusted. Moreover, when the reaction is completed, the alcohol and water remaining in the decane resin can be removed by subjecting the temperature to a temperature in the range of about 60 ° C to 100 ° C under reduced pressure for about 10 minutes to 60 minutes, but The invention is not limited to this.

The alkoxy decane having an epoxy group for preparing an epoxy oxirane resin according to an embodiment of the present invention can be exemplified by the following formula 1: [Formula 1] R ¹ _n Si(OR ² ) _4-n

(wherein R ¹ is an epoxy-cycloalkyl group having one to three carbon atoms, or a straight-chain or branched alkyl group having from 1 to 6 carbon atoms and substituted with an oxirane group And R ¹ may be heteroaminated, R ² is a straight or branched alkyl group having 1 to 7 carbon atoms, and n is an integer in the range of 1 to 3.

The alkoxydecane represented by Formula 1 is not particularly limited and may, for example, include 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxy ring). Hexyl) ethyl triethyl Oxydecane, 3-glycidoxypropyltrimethoxydecane, and the like. One or a mixture of two or more types may be used.

According to an embodiment of the present invention, the epoxy oxirane resin can be prepared by a free alkoxy decane having one epoxy group, but can also be an alkoxy group having one epoxy group. The decane is prepared by hydrolysis and condensation reaction of a different type of alkoxy decane, and is not limited thereto.

The different types of alkoxy silane-based may be selected from the group consisting of alkoxy silane-sum in the formula represents at least one of: [Formula _{^{2] R 3 m Si (OR}} 4) 4-m

(wherein R ³ may include at least one functional group selected from the group consisting of: an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, having 3 An alkenyl group to one of 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, an acryl group, a methacryl group, a halogen group, an amine group a mercapto group, an ether group, an ester group, a carbonyl group, a carboxyl group, a vinyl group, a nitro group, a fluorenyl group and an alkyd group, and the R ⁴ group is a straight chain or a branched alkyl group having 1 to 7 carbon atoms, and m It is an integer in the range of 0 to 3.)

The alkoxydecane represented by Formula 2 is not particularly limited and may, for example, include tetramethoxydecane, tetraethoxydecane, methyltrimethoxydecane, methyltriethoxydecane, methyltri Propoxy decane, dimethyl dimethoxy decane, dimethyl diethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, diphenyl dimethoxy decane, diphenyl Diethoxy Decane, triphenylmethoxydecane, triphenylethoxydecane, ethyltriethoxydecane, propylethyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, Vinyl tripropoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyltrimethoxydecane, N-3-propenyloxy-2-hydroxypropyl )-3-aminopropyltriethoxydecane, N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyltripropoxydecane, 3-propenyloxypropane Methyl bis(trimethoxy)decane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, 3-propenyloxypropyltripropoxy Decane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 3-(methyl)acryloxypropyltricarboxylate Propoxydecane, N-(aminoethyl-3-aminopropyl)trimethoxynonane, N-(2-aminoethyl-3-aminopropyl)triethoxydecane, 3- Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, chloropropyltrimethoxydecane, chloropropyltriethoxy Alkoxy, heptadecafluoro - decyl trimethoxy Silane like. One or a mixture of two or more types may be used.

The composition for forming a hard coat layer according to an embodiment of the present invention may further comprise an acrylate oligomer to improve hardness.

The acrylate oligomer according to the embodiment of the present invention is not particularly limited, and may include a polyester acrylate oligomer, an urethane acrylate oligomer, an epoxy acrylate oligomer. Polymer, polyether acrylate oligomer, and the like. Preferably, a urethane acrylate oligomer can be used.

Hereinafter, the case of the urethane acrylate oligomer will be explained in detail, but the present invention is not limited thereto.

The urethane acrylate oligomer according to an embodiment of the present invention may have 6 to 9 functional groups. When the number of functional groups is less than 6, the effect of improving hardness is poor, and when the number of functional groups is more than 9, excellent hardness is obtained, but viscosity is increased.

The urethane (meth) acrylate oligomers conventionally known in the related art can be used herein without limitation. Preferably, an aminocarboxylic acid prepared by reacting a compound having at least one isocyanate group in its molecule with a (meth) acrylate compound having at least one hydroxyl group in its molecule can be used. Ester (meth) acrylate oligomer.

Specific examples of the compound having at least one isocyanate group in its molecule include at least one selected from the group consisting of 4,4'-dicyclohexyl diisocyanate, hexamethylene diisocyanate trimer, 1 ,4-diisocyanato butane, 1,6-diisocyanatohexane, 1,8-diisocyanatooctane 1,12-diisocyanatodecane, 1,5-diisocyanato-2-methylpentane, trimethyl-1,6-diisocyanatohexane, 1,3- Bis(isocyanatomethyl)cyclohexane, trans-1,4-cyclohexene diisocyanate, 4,4'-methyl bis(cyclohexyl isocyanate), isophorone diisocyanate , toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, xylene-1,4-diisocyanate, tetramethylxylene-1,3-diisocyanate, 1-chloromethyl-2, 4-diisocyanate, 4,4'-extended methyl-bis(2,6-dimethyl-phenylisocyanate), 4,4'-oxybis(phenylisocyanate) (4,4'-oxybis ( Phenyl isocyanate)), a trifunctional isocyanate derived from hexamethylene diisocyanate, toluene diisocyanate and trihydroxyl Adduct of propane, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, trifunctional isocyanate derived from isophorone diisocyanate, and hexamethyl Hexamethylene diisocyanate biuret.

Specific examples of one of the (meth) acrylate compounds having at least one hydroxyl group in its molecule include at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, (methyl) 2-hydroxy-isopropyl acrylate, 4-hydroxybutyl (meth) acrylate, A caprolactone modified hydroxy acrylate, a pentaerythritol tri/tetra(meth) acrylate mixture, and a dipentaerythritol penta/hexa (meth) acrylate mixture.

The molecular weight of the acrylate oligomer according to the embodiment of the present invention is not particularly limited and, for example, may be in the range of 500 to 100,000. When the weight average molecular weight is less than 500, the effect of improving the hardness is inferior, and when the weight average molecular weight is more than 100,000, the viscosity is increased, and thus the workability during coating is lowered.

The content of the acrylate oligomer according to the embodiment of the present invention is not particularly limited, and for example, 5% by weight to 70% by weight of the acrylate oligomer may be included based on the total weight of the composition. When the content of the acrylate oligomer is less than 5% by weight, the effect of improving cracking and bending deformation due to shrinkage generated during curing is low, and when the content of the acrylate oligomer is more than 70% by weight, the improvement is improved. The effect of hardness is suppressed.

The composition for forming a hard coat layer according to an embodiment of the present invention may further include a reactive monomer having a functional group crosslinkable with the above epoxy oxirane resin to increase flexibility.

The reactive monomer according to the embodiment of the present invention is not particularly limited, and one of the acrylic monomers generally used in the related art can be used. Preferably, a polyfunctional (meth) acrylate monomer can be used to improve a surface hardness.

Specific examples of the reactive monomer include 2-ethylhexyl acrylate, octadecyl acrylate, isodecyl acrylate, 2-phenoxyethyl acrylate, lauryl acrylate, octadecyl acrylate Ester, behenyl acrylate, tridecyl methacrylate, nonylphenol ethoxylate monoacrylate, β-carboxyethyl acrylate, isophthalic acid acrylate Isobornyl acrylate, Tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, 4-butyl-cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate Dicyclopentenyl oxyethyl acrylate), ethoxyethoxy ethyl acrylate, ethoxylated monoacrylate, 1,6-hexanediol diacrylate, triphenylethylene glycol Triphenyl glycol diacrylate, butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol Diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, three Ethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, ethoxylated neopentyl glycol Acrylate, trimethylolpropane tripropylene Ester, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, ethoxylated triacrylate, tris(2-hydroxyl) Tris(2-hydroxyethyl)isocyanurate triacrylate, dipentaerythritol pentaacrylate, bis(trimethylol)propane tetraacrylate, alkoxylated tetraacrylate And, or the like, and preferably, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, and the like. One or a mixture of two or more types may be used.

The content of the reactive monomer according to the embodiment of the present invention is not particularly limited, and for example, 1% by weight to 70% by weight of the reactive monomer may be included based on the total weight of the composition. When the content of the reactive monomer is less than 1% by weight or more than 70% by weight, it is difficult to obtain an effect of sufficiently improving flexibility.

The composition for forming a hard coat layer according to an embodiment of the present invention further includes a polymerization initiator.

Examples of the polymerization initiator include a photoradical polymerization initiator generally used, a photo-cationic polymerization initiator, a thermal polymerization initiator or the like. One or a mixture of two or more types may be used.

Examples of the photoradical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorene, hydrazine. Fluorone, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methyl-acetophenone, 4-chloro-benzophenone, 4,4'-dimethoxy Benzophenone, 4,4'-diaminobenzophenone, Mihira ketone, benzhydryl propyl ether, benzoin ethyl ether, benzyl Benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane 1-ketone, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinylpropan-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2-benzyl 1-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- Methyl propan-1-one and the like.

Examples of the photo-cationic polymerization initiator include, but are not limited to, onium salts and/or organometallic salts, or the like. For example, a diaryl iodonium salt, a triarylsulfonium salt, an aryl diazonium salt, an iron-aromatic hydrocarbon complex or the like can be used.

More specifically, examples of the photo-cationic polymerization initiator include: aryl sulfonium hexafluoroantimonate salt, aryl hexafluorophosphate (aryl) Sulfonium hexafluorophosphate salt, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, xylyl iodonium hexafluorophosphate, 9-(4-hydroxyethoxyphenyl hexafluorophosphate A 9-(4-hydroxyethoxy phenyl)thianthrenium hexafluorophosphate salt, or the like, since citrate may cause environmental problems, it is preferred to use a hexafluorophosphate-based initiator. One or a mixture of two or more types may be used.

Examples of the thermal polymerization initiator include: 3-methyl-2-butenyltetramethylammonium hexafluoroantimonate, cesium trifluoromethanesulfonate, cesium trifluoromethanesulfonate, trifluoromethanesulfonate Barium salt, barium trifluoromethanesulfonate, barium trifluoromethanesulfonate, tetrabutylphosphonium methanesulfonate, ethyltriphenylphosphonium bromide, benzyldimethylamine, dimethylamine Methyl phenol, triethanolamine, N-n-butylimidazole, 2-ethyl-4-methylimidazole, and the like. One or a mixture of two or more types may be used.

The content of the polymerization initiator according to the embodiment of the present invention is not particularly limited, and for example, 0.1 to 10 parts by weight of the polymerization initiation may be included based on 100 parts by weight of the epoxy siloxane resin. Agent. When the content of the polymerization initiator is in the above range, the excellent curing efficiency of the composition can be maintained, and deterioration of physical properties due to the remaining components after curing can be prevented.

The composition for forming a hard coat layer according to an embodiment of the present invention may further include an antioxidant for suppressing an oxidation reaction caused by the polymerization initiator, as needed.

The antioxidant is not particularly limited, and examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, amine antioxidants, thioester antioxidants, and the like.

Specific examples of the phenolic antioxidant include: tetra-[methyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,2-bis (3,5) -1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, thiodiethylidene bis[3 -(3,5-Di-tert-butyl-4-hydroxyphenyl)propionate](thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), 3- (8,5-di-t-butyl-4-hydroxyphenyl)propionic acid octadecyl ester, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Trialkyl ester, N,N ' -hexamethyl-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamoguanamine), phenylpropionic acid, 3,5-bis (1,1- Dimethylethyl)-4-hydroxyphenylpropionic acid thiodi-2,1-ethanediester, C7-9-branched alkyl ester, 2,2 ' -ethylene bis (4, 6-di-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 4, 6-bis(octylthiomethyl)-o-cresol, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tributylbenzyl)isocyanurate, 2,2 '- extending methylenebis (4-methyl-6-tertiary-butylphenol), triethylene glycol - bis-3- (3 of Butyl-4-hydroxy-5-methylphenyl)propionate, 2,5-di-third amyl-hydroquinone, hexamethylene bis[3-(3,5-di- Tributyl-4-hydroxyphenyl)propionate], tris-(3,5-di-t-butylhydroxybenzyl)isocyanurate, 4,4 ' -thiobis(6- tributyl - m-cresol), 4,4 '- extending butyl bis (6-tert-butyl-3-methylphenol) and the like.

Specific examples of the phosphorus antioxidant include: tris(2,4-di-tert-butylphenyl)nonyl (tris(2,4-di-tert-butylphenyl)nonyl), distearyl decyl pentaerythritol dioxime Distearyl pentaerythritol dinonyl, bis(2,4-di-t-butylphenyl)pentaerythritol dinonyl, triphenylsulfonyl, triisodecylsulfonyl, diphenylisodecylsulfonyl, 2 Ethylhexyldiphenylfluorenyl, poly(dipropylene glycol)phenylindenyl, tris(nonylphenyl)fluorenyl, and the like.

Specific examples of the amine antioxidant include: 2,2,4-trimethyl-1,2-dihydroquinoline oligomer, and sulfur Specific examples of the ester antioxidant include pentaerythrityl tetrakis (3-laurylthiopropionate), di(octadecyl) thiodipropionate, and thiodipropionic acid. Dilauryl ester, ditridecyl thiodipropionate, and the like.

The content of the antioxidant according to the embodiment of the present invention is not particularly limited. For example, 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of the epoxy siloxane resin Parts, preferably 1 part by weight to 8 parts by weight, and more preferably 3 parts by weight to 6 parts by weight of the antioxidant. When the content of the antioxidant is less than 0.1 part by weight, the effect of oxidation resistance is low, and thus heat resistance may be lowered. When the content of the antioxidant is more than 10 parts by weight, heat resistance is also lowered due to auto-oxidation of the antioxidant.

A composition for forming a hard coat layer according to an embodiment of the present invention further includes a solvent.

The solvent according to the embodiment of the present invention is not particularly limited, and one solvent known in the related art can be used. Examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, methyl cellosolve, ethyl cyanoside or the like; ketones such as methyl ethyl ketone and methyl butyl Ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, cyclohexanone or the like; hexanes such as hexane, heptane, octane, or the like; benzenes such as benzene, toluene , xylene, etc. One or a mixture of two or more types may be used.

The solvent content according to the embodiment of the present invention is not particularly limited, and for example, 20 parts by weight to 70 parts by weight of the solvent may be included based on 100 parts by weight of the epoxy siloxane resin. When the content of the solvent is less than 20 parts by weight, the viscosity is too high, and thus workability is lowered. When the content of the solvent is more than 70 parts by weight, it is difficult for a thick film to adjust the thickness of a coating during the coating process, the solvent drying time after the coating process is also prolonged, and thus the process speed is lowered, resulting in a decrease in the process speed. Low economic efficiency.

According to an embodiment of the present invention, the composition for forming a hard coat layer may further include an inorganic filler to improve hardness.

The inorganic filler is not particularly limited, and examples of the inorganic filler include metal oxides such as cerium oxide, aluminum oxide, titanium oxide or the like; hydroxides such as aluminum hydroxide, Magnesium hydroxide, potassium hydroxide or the like; metal particles such as gold, silver, copper, nickel, alloys thereof or the like; conductive particles such as carbon, carbon nanotubes, fullerene or the like; glass; ceramics Or the like, and preferably, the inorganic filler may be cerium oxide. One or a mixture of two or more types may be used.

The diameter of the inorganic filler is not particularly limited, and is, for example, in the range of 1 nm to 100 nm. When the average diameter is less than 1 nm, the effect of improving the hardness is low, and when the average diameter is more than 100 nm, the inorganic filler becomes an impurity of the hard coat layer. Preferably, the average diameter can range from 10 nanometers to 30 nanometers.

The content of the inorganic filler according to the embodiment of the present invention is not particularly limited. For example, 0.1 part by weight to 5 parts by weight of the inorganic filler may be included based on 100 parts by weight of the epoxy siloxane resin. When the content of the inorganic filler is less than 0.1 part by weight, the effect of improving the hardness is low, and when the content of the inorganic filler is more than 5 parts by weight, the viscosity is increased, and thus the coatability is lowered.

According to an embodiment of the present invention, the composition for forming a hard coat layer may further include a lubricant to improve winding efficiency, blocking resistance, abrasion resistance and scratch resistance. Sex.

The type of the lubricant according to the embodiment of the present invention is not particularly limited, and examples of the lubricant include waxes such as a polyethylene wax, a paraffin wax, a synthetic wax, a montan wax or the like; a synthetic resin, For example, a polyoxyl resin or a fluorine-based resin. One or a mixture of two or more types may be used.

The content of the lubricant according to the embodiment of the present invention is not particularly limited, and for example, 0.1 part by weight to 5 parts by weight of the lubricant may be included based on 100 parts by weight of the epoxy siloxane resin. When the content of the lubricant is in the above range, it provides excellent anti-caking property, Abrasion resistance and scratch resistance, and can maintain satisfactory transparency.

Further, additives such as an antioxidant, a UV absorber, a light stabilizer, a thermal polymerization inhibitor, a leveling agent, a surfactant, a lubricant, an antifouling agent or the like may be further included as needed.

Hard coating

Moreover, the present invention provides a hard coat film 100 comprising a base material 110 having at least one surface having a hard coat layer 120 formed from a composition for forming a hard coat layer.

Preferably, the base material 110 according to an embodiment of the present invention has excellent transparency, mechanical strength, thermal stability, water resistance, isotropy, and the like. Examples of the base material 110 include base materials prepared from polyester resins such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate or And the like; a cellulose resin such as diethylidene cellulose, triethyl fluorenyl cellulose or the like; a polycarbonate resin; an acrylic resin such as poly(methyl) methacrylate, poly(methyl) acrylate Ester or the like; a styrene resin such as polystyrene, acrylonitrile-styrene copolymer or the like; a polyolefin resin such as polyethylene, polypropylene, a polyolefin resin having a ring or a norbornene structure , an ethylene-propylene copolymer or the like; a polyimine resin; a polyether oxime resin; a ruthenium resin or the like. One or a mixture of two or more types may be used.

The thickness of the base material 110 is not particularly limited and may be, for example, in the range of 20 μm to 150 μm.

The hard coat layer 120 is coated and cured by a composition for forming a hard coat layer To form, and the coating can be carried out using a conventional method, such as a die coater method, an air knife method, a reverse roll method, a spray method, a knife coating method, a casting method, a gravure method (gravure) Method), a spin coating method, and the like.

The thickness of the hard coat layer 120 is not particularly limited and may be, for example, in the range of 30 μm to 100 μm. When the thickness of the hard coat layer 120 is in the above range, a curl phenomenon hardly occurs, and the hard coat layer 120 having excellent hardness can be obtained.

The hard coat layer 120 according to an embodiment of the present invention is formed of a composition for forming a hard coat layer, and thus has a significantly improved hardness. Although the hardness may vary depending on the content, type or the like of each composition, the pencil hardness of the hard coat layer 120 may be 5H or more, and when each of the above compositions is mixed at an intended content The maximum pencil hardness of the hard coat layer 120 may be 9H or higher than 9H.

Moreover, the flexibility is remarkably enhanced, and thus the bending deformation is small.

The hard coat film 100 has a high surface hardness, including the hard coat layer 120 having excellent flexibility, and thus has lighter and superior impact resistance than the tempered glass. Therefore, the hard coat film 100 can be preferably used as one of the window substrates at the outermost surface of the display panel.

Moreover, the present invention provides an image display device including a hard coat film 100.

The hard coat film 100 can be used as a window substrate at the outermost surface of the image display device, and the image display device can include various image display devices commonly used, such as a liquid crystal display device, an electroluminescence display device, and an electric A slurry display device, a field emission display device, and the like.

Hereinafter, the present invention will be explained in detail in conjunction with the examples.

Preparation Example 1

2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) And water (H ₂ O, manufactured by Sigma-Aldrich Corporation) was mixed at a ratio of 24.64 g: 2.70 g (0.1 mol: 0.15 mol), and then placed in a 250 ml 2 In the neck flask. Next, 0.1 ml of tetramethylammonium hydroxide was added as a catalyst and 100 ml of methyl ethyl ketone (MEK) to the mixture, and stirred at 60 ° C for 36 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 2

2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Silane (ECTMS, from Tokyo Kasei Kogyo Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Corporation) in 24.64 g: 2.70 One ratio of gram (0.1 mole: 0.15 mole) was mixed and then placed in a 250 ml 2-neck flask. Next, 0.1 ml of tetramethylammonium hydroxide was added as a catalyst and 50 ml of MEK to the mixture, and stirred at 70 ° C for 24 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 3

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.), phenyltrimethoxydecane (PTMS, manufactured by Sigma Aldrich), and water (H ₂ O, manufactured by Sigma Aldrich) was mixed at a rate of 12.32 g: 12.02 g: 2.70 g (0.05 mTorr: 0.05 mol: 0.15 mol), and then placed in a 250 ml 2-neck flask in. Next, 0.1 ml of tetramethylammonium hydroxide was added as a catalyst and 50 ml of MEK to the mixture, and stirred at 80 ° C for 24 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 4

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Co., Ltd.) were 24.64 g: A ratio of 2.70 grams (0.1 mole: 0.15 moles) was mixed and placed in a 100 ml 2-neck flask. Next, 0.1 ml of tetramethylammonium hydroxide was added as a catalyst to the mixture, and stirred at 60 ° C for 24 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 5

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Co., Ltd.) were 24.64 g: A ratio of 2.70 grams (0.1 mole: 0.15 moles) was mixed and placed in a 100 ml 2-neck flask. Next, 0.1 ml of tetramethylammonium hydroxide was added as a catalyst to the mixture, and stirred at 80 ° C for 24 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 6

3-glycidoxypropyltrimethoxysilane (GPTS, manufactured by Sigma Aldrich) and distilled water were mixed at a ratio of 23.63 g: 2.70 g (1 mol: 1.5 mol). 0.02 g of sodium hydroxide was added to the mixture as a catalyst to promote the reaction, and stirred at 80 ° C for 24 hours. Next, propylene glycol methyl ether acetate (PGMEA, manufactured by Sigma Aldrich) was added to the mixture, and the mixture was made with a volatile material at 0.1 MPa and 60 using a vacuum evaporator. The reaction was carried out at ° C for 30 minutes, and the water remaining in the resin was removed, and thereby a resin was obtained.

Preparation Example 7

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Co., Ltd.) were 24.64 g: A ratio of 2.70 grams (0.1 mole: 0.15 moles) was mixed and placed in a 100 ml 2-neck flask. Next, 0.05 ml of tetramethylammonium hydroxide was added as a catalyst and 50 ml of MEK to the mixture, and stirred at 70 ° C for 36 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 8

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Co., Ltd.) were 24.64 g: A ratio of 2.70 grams (0.1 mole: 0.15 moles) was mixed and placed in a 100 ml 2-neck flask. Next, 0.5 ml of tetramethylammonium hydroxide was added as a catalyst and 50 ml of MEK to the mixture, and stirred at 70 ° C for 24 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 9

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.), phenyl trimethoxysilane (PTMS, manufactured by Sigma Aldrich) And water (H ₂ O, manufactured by Sigma Aldrich) mixed at a ratio of 11.09 g: 13.22 g: 2.70 g (0.045 m: 0.055 m: 0.15 m), and then placed in a 250 ml In a 2-neck flask. Next, 0.1 ml of tetramethylammonium hydroxide was added as a catalyst and 50 ml of MEK to the mixture, and stirred at 80 ° C for 24 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 10

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Co., Ltd.) were 24.64 g: A ratio of 2.70 grams (0.1 mole: 0.15 moles) was mixed and placed in a 100 ml 2-neck flask. Next, 0.1 ml of tetramethylammonium hydroxide was added as a catalyst and 100 ml of MEK to the mixture, and stirred at 60 ° C for 36 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 11

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Co., Ltd.) were 24.64 g: A ratio of 2.70 grams (0.1 mole: 0.15 moles) was mixed and placed in a 100 ml 2-neck flask. Next, 1.0 ml of tetramethylammonium hydroxide was added as a catalyst to the mixture, and stirred at 80 ° C for 48 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 12

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Co., Ltd.) were 24.64 g: A ratio of 2.70 grams (0.1 mole: 0.15 moles) was mixed and placed in a 100 ml 2-neck flask. Next, 0.5 ml of tetramethylammonium hydroxide was added as a catalyst to the mixture, and stirred at 80 ° C for 36 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 13

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Co., Ltd.) were 24.64 g: A ratio of 2.70 grams (0.1 mole: 0.15 moles) was mixed and placed in a 100 ml 2-neck flask. Thereafter, 1.0 ml of tetramethylammonium hydroxide was added as a catalyst to the mixture, and stirred at 70 ° C for 36 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Preparation Example 14

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECTMS, manufactured by Tokyo Chemical Industry Co., Ltd.) and water (H ₂ O, manufactured by Sigma-Aldrich Co., Ltd.) were 24.64 g: A ratio of 2.70 grams (0.1 mole: 0.15 moles) was mixed and placed in a 100 ml 2-neck flask. Next, 0.2 ml of tetramethylammonium hydroxide was added as a catalyst and 50 ml of MEK to the mixture, and stirred at 60 ° C for 36 hours. Next, the mixture was filtered using a 0.45 μm Teflon filter, and thereby an alicyclic epoxy oxirane resin was obtained. The molecular weight of the alicyclic epoxy oxirane resin was measured by gel permeation chromatography (GPC).

Examples and comparative examples

A composition for forming a hard coat layer having the composition and content listed in Table 2 below was prepared.

Experimental example

(1) Measurement of pencil hardness

The composition for forming a hard coat layer prepared in the examples and the comparative examples was applied to a base material which was polyethylene terephthalate and had a thickness of 188 μm, and used 365 奈A metal halide lamp of one of the meter wavelengths was cured at 300 mW/cm and 1.2 J/cm 2 and thereby formed a hard coat layer having a thickness of 50 μm. The resulting hard coat layer was placed in an oven at 130 ° C for post-cure for 30 minutes, and thereby a final product was obtained.

The hardness of the hard coat layer was measured using a pencil hardness tester in accordance with JIS K5600.

(2) Evaluation of flexibility

The base material prepared in Experimental Example 1 was wound at an angle of 180° on a cylinder having a bottom radius R ₁ and returned to the starting point in such a manner that the hard coat layer was placed on the inner side. Next, the minimum R ₁ of the cylinder in which the bending deformation (for example, folding marks, strain, whitening, cracks, or the like) of the hard coat layer was not observed was recorded.

Further, the base material was wound at an angle of 180° on a cylinder having a bottom radius R ₂ in such a manner that the hard coat layer was placed on the outer side, and returned to the starting point. Next, the minimum R ₂ of the cylinder in which the bending deformation of the hard coat layer was not observed was recorded.

Referring to Table 3, the hard coat layer prepared from the compositions of Examples 1 to 9 had a high pencil hardness. Further, such a hard coat layer was determined to have a low value of R ¹ and R ^2, in other words, the hard coat layer having excellent flexibility.

However, the hard coat layer prepared from the compositions of Comparative Examples 1 to 5 and Comparative Example 7 had significantly lower pencil hardness or reduced flexibility. Moreover, the composition of Comparative Example 6 gelled, so that it was impossible to prepare a film.

The composition according to an embodiment of the present invention can form a hard coat layer having a remarkably improved hardness.

The composition according to an embodiment of the present invention can form one hard coat layer having excellent flexibility, so that bending deformation is minimized. Therefore, including the embodiment according to the present invention includes hard The base material of the coating ensures excellent flexibility without the need for a separate bending deformation suppression layer.

It will be appreciated by those skilled in the art that various modifications of the exemplary embodiments of the invention described above may be made without departing from the spirit and scope of the invention. The invention is therefore intended to cover all modifications of the invention, which are within the scope of the appended claims and their equivalents.

100‧‧‧hard coating

110‧‧‧Basic materials

120‧‧‧hard coating

Claims (9)

A composition for forming a hard coat layer comprising an epoxy oxirane resin having a weight average molecular weight in the range of 2,000 to 15,000 and a plurality of in the range of 2.0 to 4.0 Dispersibility index (PDI). The composition of claim 1 wherein the decane resin has a weight average molecular weight in the range of from 5,000 to 15,000. The composition of claim 1 wherein the decane resin has an epoxy equivalent in the range of from 3.0 millimoles per gram to 6.3 millimoles per gram. The composition according to claim 1, wherein the decane resin is prepared by hydrolysis and condensation reaction of one of alkoxy decane represented by the following formula 1: [Formula 1] R ¹ _n Si(OR ² ) _4-n (wherein R ¹ is an epoxycycloalkyl group having 3 to 6 carbon atoms, or having 1 to 6 carbon atoms and replaced by an oxiranyl group) a chain or a branched alkyl group, and R ¹ may be heteroatomized with oxygen, R ² is a straight chain or branched alkyl group having 1 to 7 carbon atoms, and n is one of the range of 1 to 3 Integer). The composition according to claim 4, wherein the alkoxydecane represented by Formula 1 is at least one selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyl Trimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, and 3-glycidoxypropyltrimethoxysilane. The composition according to claim 4, wherein the decane resin is prepared by hydrolysis and condensation reaction of the alkoxy decane represented by Formula 1 and one alkoxy decane represented by Formula 2: 2] R ³ _m Si(OR ⁴ ) _4-m (wherein R ³ includes at least one functional group selected from the group consisting of: an alkyl group having 1 to 20 carbon atoms, having 3 to a cycloalkyl group of 8 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, acrylic acid Acryl group, methacrylic group, halo group, amine group, mercapto group, ether group, ester group, carbonyl group, carboxyl group, vinyl group, nitro group, sulfone group and alkyd group ( Alkyd group), R ⁴ is a straight or branched alkyl group having 1 to 7 carbon atoms, and m is an integer of 0 to 3). The composition of claim 1, further comprising 0.1 parts by weight to 10 parts by weight of one of the polymerization initiators and 20 parts by weight to 70 parts by weight based on 100 parts by weight of the epoxy oxirane resin. A solvent. A hard coating film comprising a base material, at least one surface of which has a hard coat layer formed from the composition according to any one of claims 1 to 7. The hard coat film according to claim 8, wherein the base material is made of at least one resin selected from the group consisting of a polyester resin, a cellulose resin, and a polycarbonate resin. An acrylic resin, a styrene resin, a polyolefin resin, a polyamidene resin, a polyether oxime resin, and a fluorene resin.